Hydraulic cement compositions



EXAMlNER UNITED STATES PATENT .-OFFlCE HYDRAULIC CEMENT COMPOSITIONS Edward W. Scripture, J r., Cleveland, Ohio, assignor to The Master Builders Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application November 29, 1951, Serial No. 258,980

3 Claims. (Cl. 106-90) This invention relates to hydraulic cement compositions, and particularly to 3 ment concrete or mortar mixes and ad ive compositions for modifying the properties thereof.

Among the desirable characteristics of hydraulic cement mixes for certain uses, in addition to high ultimate strength, are high early strengths and rapid initial set to permit early finishing of the surface, as by troweling, and early load sustaining properties. These characteristics are particularly desired when the cement mixes are to be used in constructing concrete floors and other paved areas.

The principal object of the present invention is to provide hydraulic cement concrete or mortar mixes that have a shortened finishing time, i. e., that rapidly harden sufficiently ed to give tlfides'ired surface texture, that also ave good earl strength and resistance to the 2 if ts strength.

Another object of the invention is to provide compositions for addition to hydraulic cement mixes for accomplishing the foregoing objective.

Unmodified hydraulic cement concretes do not stand up well when subjected to freezing and thawing conditions in the colder climates and to attack by salts used for de-icing, and additives for increasing the resistance of concretes to such conditions have also been employed for a number of years. These additives are known as air entraining agents.

Other additives have been employed to increase the ultimate strength of hydraulic cement ,-'mixes, and the most widely used compositions for this purpose are known as cement agents. These aggnts iemi t lasticize e cement mixes, thus reducin the amount of ajenrequired to prodlmi'xes of a required plasticity, and the resulting reduction in the watercement ratio incre u str the hardeneg ggncretes.

--6ne"oi"the problems that has arisen in the 45 use of additives for various purposes is that their use to improve cement mixes in certain respects has generally produced concretes that are inferior in other respects. Attempts to use a multiplicity of additives to obtain the beneficial effect of each and counteract the deleterious effects of each other have often been unsuccessful.

What are believed to be the first cement dis- 2 in U. S. Patent No. 2,1i1,569, granted to George R. Tucker, December 27, 1938. These compositions are organic compounds of the type resulting from the End optionally neutralizing the reaction producd'.

with an alkali or alkaline earth hydroxide to produce a soluble salt form of the condensation product. 'The most conveniently produced compounds of this class, and the ones apparently preferred by Tucker for this reason, are compounds produced by g g or its equivalent wit na t alene sul ho 0 acid or its homologues or derivatigs and optionally neutralizmg the condensation roduct to conve'T the compounds to soluble salts. Tucker proposed that such condensation prdducd; be used in amounts of from 0.1% to 0 32, by weight of the hydraulic cemFfitT'Fdf'convenience in the following discussion, the class of compounds disclosed by Tucker will be referred to herein as Tuckers condensation produc condensin formaldeh e condensation of aromatic sulphonic acids with formaldehyde or higher a a e ydes,

Another class of cement dispersing agents consists of various waste sulfite li uor derivatives in which the active ingredient is a soluEle salt of lignosulphonic acid. My U. S. Patent" No. 2 ,I 6,9B U, granted August 15', 1939, discloses and claims hydraulic cement mixes containing the water soluble constituents of waste sulfite li uor. a en 0. ,594 to Donal MacPherson, granted February 10, 1948, discloses and claims cement mixes containing the so of waste sulfite liguo; from which the fermen a e sugars, g ucosi es, and the like present the starting material have been extracted b fermentation and removal of the refiltmg alcohols b distillation. Separation of these fermentab le materials to produce substantially equivalent waste sulfite li uo idu may also be accomplished by known chemical processes and by the action of certain yeast that feed on the fermentable materials and consume them without converting them to alcohols. For convenience, the solids of waste sulfite liquor remainin after the removal of fermentable materials by one process or another are referred to Herein as desugarized waste sulfite liquor solids, it being understood that the term sugars is used broadly in this connection to include the various fermentable materials having certain sugar-like properties.

Tuckers condensation product and the plain and desugarized waste sulfite liquor solids have somewhat similar cement dispersing properties,

persing agents known to the art were disclosed and also entrain substantial amounts of air.

3 Though known in the art for use in accomplishing the same general results, they do not accomplish those results to the same degree and are not equivalents in their efiects upon the physical properties of cement mixes.

While Tuckers'condensation product and its many variants do reduce the amountof water required to produce a cement mix having a given plasticity, they do not materially increase the ultimate strength of the hardened cementmix, as might be expected from the reduction in the water-cement ratio, and they have little or no effect on early strengths at from 1 to 3 days. Also, they are only fair air entraining agents. As a result, Tucker's condensation product and its variants have met with substantially nocomi mercial use.

Unmodified waste sulfite liquor solids, when used in amounts of from 0.15% to 0.3% By weight of the hydraulic cement, materially increase the ultimate strengthof cement mixes. By reason of the air lting from their use, they also increase resistance to destruction from freezing and thawing and counteract the scaling effects of de-icing with various salts. Thus, this type of cement additive has gone into extensive commercial use. However, it has the drawback for certain uses, particularly for floors and outdoor paving, of greatly retarding the initial set and the rate of gain of strength with age. This retarding action is substantial at normal temperatures and is even more pronounced at low temperatures. Consequently, the use of this type of additive has been objectionable where rapid initial set and high early strength are desired. This is particularly so in the case of cement floors and paved areas because of the delay encountered before the cement mix has set sufliciently for surface finishing and before it is capable of carrying any appreciable loads.

The desugarized waste sulfite 1i uor solids of MacPherson are superior to unmodified waste sulfite liquor solids as regards the early strength of cement mixes containing them, and they produce an actual increase in strength as early as about 3 to '7 days. However, they still cause about a 50% reduction in strength at one day and substantially prolong the finishing time. (See Example 2 of the MacPherson patent.)

As regards the finishing time, Tuckers condensation product is not objectionable and actu ears to s orten the finishing time slightly in-some -instances... However, this effect is so slight, at best, that it is inconsequential, and the relatively inferior air entraining properties and cement dispersing proper ms suc compounds have rendered them commercially unsatisfactory for any purpose up to this time.

While the finishing time of cement mixes may be shortened by the use of substantial amounts of an accelerator, such as calcium chloride, the

use of calcium chloride in sufiicient amount to counteract the early retarding effects of the various waste sulfite liquors is believed to aggravate reaction between high alkali cements and reactive aggregates and to have other undesirable efl'ects, such as excessive heat evolution and volume change duringsetting of the cement. Such soluble salts also tend to increase efliorescence of the hardened concrete.

In accordance with the present invention, I have discovered that the finishing time and early rate of gain of strength may be greatly improved by incorporating in the cement mixes a combination of a condensatiog prgduct 2f thelype 4 d s o y. Teete gesii erize .w s s te liquor solids, each being used in an amount somevvfiat'lessthan has been previously recommended when used separately for their air entraining 5 and cement dispersing effects. .{I'he amounts of these materials previously considered to be the optimum for most purposes when used individually, do not shorten the finishing time or increase the rate of gain of strength when such amounts of each are combined in the same mix. Surprisingly, however, when these materials are employed together in somewhat lesser amounts, the initial set is substantially accelerated and the finishing time corespondingly reduced. This is unexplainable from anything heretofore known regarding the behavior of these materials. The amounts of these two materials which I prefer to employ in combination, produces, when used separately, little or no effect on the finishing time in the case of Tuckers condensation product and a substantially greater finishing time and slower initial set in the case of desugarized waste sulfite liquor solids. Why the combination of these materials in such amounts results in a substantial decrease in the finishing time is something which I am as yet unable to explain. However, the behavior of the materials, alone and in combination, may be illustrated by comparative tests as follows:

A series of concrete mixes was prepared with the same cement and aggregate, each having a nominal cement factor of 6 sacks per cu. yd. of concrete and a slump of 6 inches determined by the standard A. S. T. M. method. One mix contained no additives and served as a control. Two contained different amounts of desugarized waste sulfite 1i uor (designated desug. W.'S."E'."'$ as the only additive, and two contained d'fi'i erent mined at 70 F. The results of these tests are set forth in Table I.

Table I Finishing Additive a; at

None.

0.16% desug. W. S. L

0.27% desug. W. S. L 0.11% Tucker 0-? 0.27% Tucker O-P From the foregoing data it will be noted that the desugarized waste sulfiteliquor prolonged to the finishing time "from 13% to"'20%, and that Tuckerls condensatign grgduct reduced the finishing time about 7%. h V V In a similar set of tests the combination of 0.2% desugarized waste sulfite liquor and 0.25% of Tuckers condensation product merely entrained an excessive amount of air, giving a relatively weak concrete and no noticeable acceleration of the finishing time.

In still another set of similar tests, however, in which the desugarized waste sulfiteliquor and r eigenstates with one containing desugarized waste sulfite liquor plus calcium chloride and another control containing no additive, a surprisipg aggelgratiqn twist-e WM wefe" combined in smaller amounts in the same mix and compared of the initial set together with unusual ultimate strength were obtained. These results are shown in Table 11.

As shown in Table II, the use of desugarized waste sulfite liguor in combination with calcium chloride in the second test still prolonged the finishing time, though producing about the expected gain in ultimate strength. But when the desugarized waste sulfite liquor in smaller amount was com me w1 a si smaller amount of Tucker's condensation product in the third test, the finishing time at 70 F. was reduced about 8% while obtaining even higher ultimate strength than in the second test.

These last results are surprising in two respects, viz. the combination of one ingredient that prolongs and another that only slightly reduces the finishing time results in a far greater reduction in finishing time than the most efl'ective of the two ingredients when used separately, and the combination of one ingredient that substantially increases ultimate strength with another that is relatively inefiective-for that purpose results in a greater, rather than a lesser ultimate strength.

When employing the present invention, the

/ condensation product used may be varied widely where R is hydrogen or a straight or branched chain aliphatic radical, A and A are the same or difierent aromatic radicals, M is hydrogen, an alkali or alkaline earth metal, or other solubilizing, salt-forming radical such as amine radicals, a: is 0 or an integer from 1 to about 3, and y is an integer from 1 to about 3. The class may ,--be generically described as consisting of the water-soluble products of condensation of sulfonated aromatic hydrocarbons with aliphatic aldehyd es and the water-soluble salts of 'such condensation pro uc s. Examples of suc compounds, which I have found to be suitable for use in the present invention, include the acid form or the products of condensing an aliphatic aldehy e, suc as orma ehyde, acetaldehyd'e. e c., with na htha ene sulfonic acid with meth [Ea hthalene sulfonic acid' the odium pgtassium, calcium, and ammonium salts of'such condensation roficts; and the dimethylamine and diethylamine salts of such con ensatio pro uc 77s is apparent, the nature of the soluiizing radical is of no particular significance nd plays no part in controlling the character of the results achieved. Also, the number of carbon atoms in the aliphatic aldehyde is immaterial except as limited by the requirement that the final condensation product be water-soluble. While the invention involves the use of Qe; sugarized waste sulfite liquor solids, as defined -aliiove'fit will also be understood that these solids may be retained in a liquid medium or placed in a ligulgi medirrg r before or at the time of incorporating them into a cement mix.

I have also found that the incorporation in the composition of a small amount of an accelerator such as calcium chloride, sodium s' 1 or potassium bichromate will urther improve" the rop ies o e mix, particularly with respect to finishing time and early strength. Thus, my preferred indurating composition comprises 0.11%

of waste sulfite liguor, 0.08% of naphthalene sul; phonic acid, forma dehyde condensate, and 0.09%

of caldlum chl v all based on the weight of the cemen A T e results obtained with such a composition are given in Table III, where they are compared with the results from the same basic mix containing no additives and from the same basic mix containing conventional amounts of desugarized wa te ..ulfite liquor solids and calcium chloride as the only additives. To illustrate how lower curing temperatures magnify the differences in finishing time, finishing tests were made in this case at both F. and 45 F.

When the two principal additives are used in combination in accordance with the present invention, from about 0.05% to 0.25% of desugarized waste sulfite li uor solids and from 0.05% to 0.20% of the condensation product by weight based on the cement, are suitable for most purposes, though there are no critical limits. Amounts either below or above these ranges have insuificient accelerating action, or none at all, and larger amounts also reduce the early strengths and, by entraining an excessive amount of air, reduce the ultimate strength to a degree that is generally unsatisfactory.

The relative amounts of the two types of additives are also important. I preferably employ from about 1 to 3 parts of the condensation produc t to 3 parts of desugarized waste sulfite liquor solids. Where the two additives are presentiii equal amounts, they should not exceed about 0.20% each, by weight based on the cement. With lower amounts of the condensation product, the amount of desugarized waste sulfite liquor may run as high as the maximum of 0.25% indicated above, with good results. When calcium chloride is also included, the amount of the condensation product relative to the amount of desugarized waste sulfite liguor should be kept well cement before grinding and be ground thereknown air entrainin a ents, such as sodium M lauryl sulphate, or tall oil, or air entraining agents c as escri ed in "'my copending application Serial No. 60,635, filed November 1'7, 1948, for Cement Composition and Indurating Composition Therefor, Patent No. 2,593,492, may be incorporated in the compositionor in the concrete mix to increase the entrained air content to the percentage desired.

Similarly, where maximum ultimate strength is desired and freezing conditions are not likely to be encountered, the entrainment of air may be undesirable and a suitable air detrainin agent may be incorporated in a'cement mix with the additives of the present invention. A large number of air detraining agents, which are liquid organic'ompoungs characterized by water-inso u i ity and the presence of both a lyophilio cup and a hydrocarbon lyophobic group are 51s closed in my copending With No. 90,549, filed April 29, 1949, for Cement Compositions, now abandoned.

The additives employed in accordance with this invention, including calziilurmm h lgitmr-atber accelerator, as well as st er additives, may all be mixed together in the form of dried powders, or they may be utilized dissolve r.

is not necessary that the desugarized waste sulfite liquor be secured in the first instance in the dried form, but it is usually more convenient for handling and storage to have all the ingredients dry. It is, however, customary to dissolve or suspend additive compositions in yateg at the location wh're the concrete is made, and to measure them and add them to the concrete in the form of a solution or suspension. The present invention may be carried out in this manner.

8 The additive composition may also be incorporated in dry form in the cement itself by intergrinding oTbTmixing the cement and composition prior to use.

Having described my invention, I claim:

1. A cement composition comprising an hydrauhc cement, from about 0.05% to 0.25% by weight of the cement of desugarized waste sulfite liquor solids, and from about 0.05% to 0.20% by weight of the cement of a member of the class consisting of the water-soluble products of condensation of sulfonated aromatic hydrocarbons with aliphatic aldehydes and the water-soluble salts of said products.

2. A cement composition comprising an hydraulic cement, from about 0.05% to 0.25% by weight of the cement of desugarized waste sulfite liquor solids, and from about 0.05% to 0.20% by weight of the cement of a member of the class consisting of the water-soluble products of condensation of sulfonated aromatic hydrocarbons' with aliphatic aldehydes and the watersoluble salts of said products, there being from about 1 to 3 parts of a member of said class to 3 parts of desugarized waste sulfite liquor.

3. A cement composition comprising an hydraulic cement, from about 0.05% to 0.15% each, by weight of the cement of desugarized waste sulfite liquor solids, as one additive, a member of the class consisting of the water-soluble products of condensation of sulfonated aromatic hydrocarbons with aliphatic aldehydes and watersoluble salts of said products, as a second additive, and calcium chloride as a third additive, said second and third additives being present in the proportions of about 1 to 2 parts of each to 2 parts of said first additive.

References Cited inthe file of this patent UNITED STATES PATENTS Number Name Date 2,141,569 Tucker Dec. 27, 1938 2,141,571 Kennedy Dec. 27, 1938 2,383,891 Scripture Aug. 28, 1945 2,435,594 MacPherson Feb. 10, 1948 2,485,102 MacPherson Oct. 18, 1949 

1. A CEMENT COMPOSITION COMPRISING AN HYDRAULIC CEMENT, FROM ABOUT 0.05% TO 0.25% BY WEIGHT OF THE CEMENT OF DESUGARIZED WASTE SULFITE LIQUOR SOLIDS, AND FROM ABOUT 0.05% TO 0.20% BY WEIGHT OF THE CEMENT OF A MEMBER OF THE CLASS CONSISTING OF THE WATER-SOLUBLE PRODUCTS OF CONDENSATION OF SULFONATED AROMATIC HYDROCARBONS WITH ALIPHATIC ALDEHYDES AND THE WATER-SOLUBLE SALTS OF SAID PRODUCTS. 